CN105377787A - Laminated glass interlayer and laminated glass - Google Patents
Laminated glass interlayer and laminated glass Download PDFInfo
- Publication number
- CN105377787A CN105377787A CN201480039947.1A CN201480039947A CN105377787A CN 105377787 A CN105377787 A CN 105377787A CN 201480039947 A CN201480039947 A CN 201480039947A CN 105377787 A CN105377787 A CN 105377787A
- Authority
- CN
- China
- Prior art keywords
- recess
- mentioned
- intermediate film
- laminated
- resin layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000005340 laminated glass Substances 0.000 title claims abstract description 166
- 239000011229 interlayer Substances 0.000 title abstract description 11
- 239000010410 layer Substances 0.000 claims abstract description 141
- 229920005989 resin Polymers 0.000 claims abstract description 91
- 239000011347 resin Substances 0.000 claims abstract description 91
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 93
- 229920002554 vinyl polymer Polymers 0.000 claims description 71
- 239000004902 Softening Agent Substances 0.000 claims description 50
- 239000011241 protective layer Substances 0.000 claims description 40
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 28
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 24
- 239000005357 flat glass Substances 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- 238000007872 degassing Methods 0.000 abstract description 4
- 150000001241 acetals Chemical class 0.000 description 83
- 239000002585 base Substances 0.000 description 43
- 238000000034 method Methods 0.000 description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 description 17
- 229920002451 polyvinyl alcohol Polymers 0.000 description 17
- 239000011521 glass Substances 0.000 description 16
- 150000001299 aldehydes Chemical class 0.000 description 14
- 238000010943 off-gassing Methods 0.000 description 14
- -1 poly(vinylidene fluoride) Polymers 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 238000002788 crimping Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000010023 transfer printing Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000003750 conditioning effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 4
- 238000005816 glass manufacturing process Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004049 embossing Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000004439 roughness measurement Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- OXQGTIUCKGYOAA-UHFFFAOYSA-N 2-Ethylbutanoic acid Chemical compound CCC(CC)C(O)=O OXQGTIUCKGYOAA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000005322 wire mesh glass Substances 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005480 shot peening Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
- C03C27/06—Joining glass to glass by processes other than fusing
- C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10559—Shape of the cross-section
- B32B17/10577—Surface roughness
- B32B17/10587—Surface roughness created by embossing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Joining Of Glass To Other Materials (AREA)
- Laminated Bodies (AREA)
Abstract
The purpose of the present invention is to provide a laminated glass interlayer and a laminated glass that includes the laminated glass interlayer, the laminated glass interlayer comprising two or more layered resin layers, having excellent degassing properties during a laminated glass production process, and being capable of preventing the occurrence of ghost images. The present invention is a laminated glass interlayer comprising two or more layered resin layers, at least one surface of the laminated glass interlayer having a plurality of concave portions and a plurality of convex portions. Bottom portions of the concave portions have continuous groove shapes, and adjacent concave portions are parallel and arranged regularly in lines. On the surface that has the plurality of concave portions and the plurality of convex portions, the groove depths (Rzg) of the concave portions as measured in accordance with JIS B-0601 (1994) are 10-40(mu)m. When any one concave portion is selected, the difference between the interval between said one concave portion and a concave portion adjacent thereto and the interval between said one concave portion and the other concave portion adjacent thereto is larger than 50(mu)m. Further, the interval between adjacent concave portions is 1000(mu)m or less.
Description
Technical field
The present invention relates to intermediate film for laminated glasses and the laminated glass containing this intermediate film for laminated glasses, described intermediate film for laminated glasses is the intermediate film for laminated glasses of the resin layer being laminated with more than 2 layers, it has excellent out gassing in the manufacturing process of laminated glass, further, ghost image can be prevented.
Background technology
Following laminated glass is used widely in the window-glass of automobile, aircraft, buildings etc., described laminated glass is the intermediate film for laminated glasses clipped between 2 pieces of sheet glass containing plasticized polyvinyl butyral, and the laminated glass making it mutually bonding and obtain.
Intermediate film for laminated glasses is not merely made up of the resin layer of 1 layer, also can be made up of the duplexer of the resin layer of more than 2 layers.By the resin layer as more than 2 layers, there is the first resin layer and the second resin layer, and the first resin layer and the second resin layer have different character, thus can provide have only 1 layer time the intermediate film for laminated glasses of various performances that is difficult to realize.
For example, Patent Document 1 discloses the intermediate film for laminated glasses of the 3-tier architecture formed with 2 layers of protective layer of this pugging of clamping by pugging.In the intermediate film for laminated glasses of patent documentation 1, contain and the polyvinyl acetal resin of the affinity excellence of softening agent and the pugging of a large amount of softening agent by having, thus given play to excellent sound-proofing.On the other hand, protective layer prevents a large amount of softening agent contained by pugging from oozing out and reducing this situation of cementability between intermediate coat and glass.
But, for employ the resin layer being laminated with more than 2 layers as above intermediate film for laminated glasses laminated glass for, when the light of the visuognosis outside across laminated glass, there is following such problem: sometimes see that the image of light is ghost image.Such ghost image especially occurs significantly when the intermediate film for laminated glasses of the such sound-proofing excellence described in patent documentation 1.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2007-331959 publication
Summary of the invention
Invent problem to be solved
The present inventor etc. have inquired into and have used the reason that ghost image occurs when being laminated with the intermediate film for laminated glasses of the resin layer of more than 2 layers.Found that, its reason is the concavo-convex of the surface being formed at intermediate film for laminated glasses.
In the manufacture of laminated glass, usually, the duplexer being at least laminated with intermediate film for laminated glasses between 2 pieces of sheet glass is undertaken smoothing out with the fingers strip (exhaust degassing method) or putting into rubber bag and carry out decompression suction (vacuum outgas method) by niproll, while carry out degassed to air residual between sheet glass and intermediate coat, crimp.Then, above-mentioned duplexer such as carried out heating and pressurizing in autoclave and crimps, thus manufacturing laminated glass.In the manufacturing process of laminated glass, importantly by glass and intermediate film for laminated glasses stacked time out gassing.For the object of out gassing guaranteed when manufacturing laminated glass, be formed fine concavo-convex at least one surface of intermediate film for laminated glasses.Especially by make this concavo-convex in recess there is the continuous ditch shape (hereinafter also referred to " groove shape ") in bottom and the recess of this adjacent groove shape is parallel and form such structure regularly, thus extremely excellent out gassing can have been given play to.
Usually, during crimping in laminated glass manufacturing process, the concavo-convex meeting being formed at the surface of intermediate film for laminated glasses is caved in, and therefore, in obtained laminated glass, substantially can not become problem.Namely, when the two sides of intermediate film for laminated glasses is formed concavo-convex, sometimes the concavo-convex lines on two sides is mutually interfered and there will be the interference fringe being called as interference fringe phenomenon, but during crimping, concavo-convex meeting is caved in, so substantially do not have problem after becoming laminated glass.
But the present inventor etc. find, for the intermediate film for laminated glasses of the resin layer being laminated with more than 2 layers, to remain concavo-convex impact in the laminated glass obtained through laminated glass manufacturing process, become the reason producing ghost image.
Namely, can think and use grain roller etc. when the surface of intermediate film for laminated glasses of the resin layer being laminated with more than 2 layers is formed concavo-convex, not only formed concavo-convex on the surface of intermediate coat, and because of the pressure adding man-hour till the interface of the interlayer of resin layer all can transfer printing concavo-convex, interface becomes unsmooth.Can think: when especially forming the recess of groove shape on surface, the recess of this groove shape at the interface of interlayer also by transfer printing firmly.Can think: although during crimping in laminated glass manufacturing process, the concavo-convex meeting on the surface of intermediate coat is caved in, but be needed on the concavo-convex of the interface of interlayer still can remain, therefore, be formed at the concavo-convex of the interface of interlayer by this and the light interference phenomena that produces becomes the reason of ghost image occurs.Can think: especially in the intermediate film for laminated glasses of the such sound-proofing excellence described in patent documentation 1; formed concavo-convex at hard protective layer; now, concavo-convex being easy to is transferred to the interlayer between this protective layer and soft pugging, therefore produces ghost image especially.
If do not formed concavo-convex on the surface of intermediate film for laminated glasses, then can prevent the generation of ghost image.But if do not formed concavo-convex, then fully cannot carry out degassed when the manufacture of laminated glass, this will cause producing bubble between glass and intermediate coat, the outward appearance of infringement laminated glass.
The present invention is in view of above-mentioned present situation, object is to provide a kind of intermediate film for laminated glasses and the laminated glass containing this intermediate film for laminated glasses, described intermediate film for laminated glasses is the intermediate film for laminated glasses of the resin layer being laminated with more than 2 layers, it has excellent out gassing in the manufacturing process of laminated glass, and can prevent the generation of ghost image.
For solving the means of problem
Intermediate film for laminated glasses of the present invention is the intermediate film for laminated glasses of the resin layer being laminated with more than 2 layers, it has multiple recess and multiple protuberance at least one surface, above-mentioned recess has bottom ditch shape continuously, adjacent above-mentioned recess is arranged side by side abreast, above-mentioned have the surface of multiple recess and multiple protuberance, the trench depth (Rzg) of the recess measured according to JISB-0601 (1994) is 10 ~ 40 μm, when selecting any one recess, this recess and and the interval of a recess that adjoins of this recess, with this recess and and the difference at the interval of another recess that adjoins of this recess more than 50 μm, and adjacent recess be spaced apart less than 1000 μm.
It should be noted that, in the present invention, " there is multiple recess and multiple protuberance " at least one surface and also mean " being formed with multiple recess and multiple protuberance at least one surface ", " recess has bottom ditch shape continuously; adjacent above-mentioned recess is arranged side by side abreast " also means " recess has bottom ditch shape continuously, and adjacent above-mentioned recess is formed abreast ".
Below the present invention is described in detail.
What the present inventor etc. concentrated on studies found that, designed by the concavo-convex pattern had the surface of intermediate film for laminated glasses, even thus be laminated with the intermediate film for laminated glasses of the resin layer of more than 2 layers, out gassing and the generation preventing ghost image of excellence when also can take into account the manufacture of laminated glass, thus complete the present invention.
Intermediate film for laminated glasses of the present invention has multiple recess and multiple protuberance at least one surface.Thereby, it is possible to out gassing when guaranteeing the manufacture of laminated glass.
Can only have above-mentioned concavo-convex on a surface, but from significantly improving the aspect of out gassing, preferably have on the two sides of intermediate film for laminated glasses above-mentioned concavo-convex.
As long as above-mentioned concavo-convex shape at least has ditch shape, such as, groove shape, reticulation etc. can be used usually to give concavo-convex shape in the surface of intermediate film for laminated glasses.The shape of the above-mentioned concavo-convex shape grain roller that can be also transfer printing.
In addition, raised part also can as shown in Figure 1, and top is planeform, can as shown in Figure 2, be also nonplanar shape.It should be noted that, when the top of raised part is planeform, can impose in the plane at this top fine concavo-convex further.
And the height of each concavo-convex protuberance can be identical height, also can be different height, and for the degree of depth of the recess corresponding with these protuberances, as long as the base of this recess is continuous, can be just the identical degree of depth, also can be the different degree of depth.
In intermediate film for laminated glasses of the present invention, the above-mentioned concavo-convex recess had at least one surface has bottom ditch shape (groove shape) continuously, and adjacent above-mentioned recess is arranged side by side abreast.Usually, for the air when duplexer being laminated with intermediate film for laminated glasses between 2 pieces of sheet glass is crimped discharge difficulty, with the connectedness of the bottom of above-mentioned recess and smoothness, there is close relationship.Be set to the recess of groove shape shape arranged side by side abreast by the concavo-convex shape at least one face by intermediate coat, thus the connectedness of above-mentioned bottom can be made more excellent, significantly improve out gassing.
Fig. 1 and Fig. 2 show represent groove shape recess at equal intervals and the schematic diagram of an example of intermediate film for laminated glasses arranged side by side abreast.
The above-mentioned trench depth (Rzg) with the recess on the surface of multiple recess and multiple protuberance is 10 ~ 40 μm.By above-mentioned trench depth (Rzg) is set to more than 10 μm, thus can give play to extremely excellent out gassing, by being set to less than 40 μm, thus temperature when can make manufacture laminated glass reduces.The preferred lower limit of above-mentioned trench depth (Rzg) is 15 μm, and preferred upper limit is 35 μm, and more preferably lower limit is 20 μm, and more preferably the upper limit is 30 μm.
It should be noted that, in this specification sheets, the ditch depth (Rzg) of recess refers to, the datum length of JISB-0601 (1994) " surfaceness-definition and expression " defined is set to 2.5mm, the ditch depth that to calculate with the average line of roughness curve (becoming the line that minimum mode sets according to the sum of squares of the deviation to roughness curve) be benchmark, the ditch depth mean value of ditch number measured thus.Above-mentioned ditch number be the value that datum length is obtained divided by the interval of above-mentioned recess radix point below enter the integer behind position.When ditch number is more than 5, calculate the ditch depth at 5 places with the darkest order of the recess existed on datum length, using its mean value as the ditch depth in each datum length.When ditch number is less than 4, calculate the ditch depth of the several number of ditch with the darkest order of the recess existed on datum length, using its mean value as the ditch depth in each datum length.At least measure the ditch depth in the 5 above-mentioned each datum lengths in place, using the ditch depth (Rzg) of its mean value as recess.In addition, above-mentioned ditch depth (Rzg) carries out data processing by the numerary signal measured using surface roughness measurement device (Inc. of little Ban institute, SE1700 α) and easily obtains.
In intermediate film for laminated glasses of the present invention, when selecting any one recess, this recess and and a recess adjoining of this recess interval, with this recess and and the difference at the interval of another recess that adjoins of this recess more than 50 μm.One example of the pattern of the recess of the groove shape that the surface of intermediate film for laminated glasses has has been shown in Fig. 3.Among the recess of the groove shape shown in Fig. 3, such as, select recess 1 as a recess.For this recess 1, recess 2 and recess 3 adjoin.In intermediate film for laminated glasses of the present invention, by the interval A of recess 1 and recess 2, compared with the interval B of recess 1 and recess 3 time, this difference must be greater than 50 μm.As mentioned above, the reason that ghost image occurs is, because of formed at resin interface layer concavo-convex, light interference phenomena occurs.By being set to the certain above pattern of interval difference of adjacent recess, thus the effect of this light interference phenomena can be reduced, effectively can suppress the generation of ghost image thus.The difference at two intervals is preferably more than 100 μm, is more preferably more than 250 μm, more preferably more than 500 μm.For the upper limit of the difference at two intervals, be not particularly limited, but as described later, the maximum value at the interval of recess is 1000 μm, therefore selects within the scope of this.
In intermediate film for laminated glasses of the present invention, the upper limit at the interval of adjacent above-mentioned recess is 1000 μm.By the interval of adjacent recess is set to less than 1000 μm, and make out gassing excellent.The preferred upper limit at the interval of above-mentioned adjacent recess is 750 μm.For the lower limit at the interval of above-mentioned adjacent recess, be not particularly limited, but as mentioned above, the difference at the interval of contiguous recess is greater than 50 μm, therefore, selects within the scope of this.
In intermediate film for laminated glasses of the present invention, when selecting any one recess, if this recess and and a recess adjoining of this recess interval, with this recess and and the difference at the interval of another recess that adjoins of this recess be greater than the scope of 50 μm, then periodically can repeat the interval of recess.Such as, can repeat according to the mode being spaced apart 500 μm, 750 μm, 1000 μm, 500 μm, 750 μm, 1000 μm with recess.In addition, when periodically repeating the interval of recess, preferably the total at the interval of the recess in 1 cycle is greater than 2000 μm.Be set to above-mentioned preferable range by the total at the interval of the recess by 1 cycle, thus further can reduce the effect of light interference phenomena.In addition, when periodically repeating the interval of recess, the upper limit of the total at the interval of the recess in 1 cycle is not particularly limited.
It should be noted that, in this specification sheets, the interval of adjacent recess refers to, in the adjacent recess for bottom ditch shape continuously, and the shortest distance between the bottommost of these two recesses.Specifically, for the interval of above-mentioned recess, use opticmicroscope (such as, SONIC Inc., BS-8000III) observe the surface (range of observation 20mm × 20mm) of intermediate film for laminated glasses, the shortest distance between the bottommost measuring all observed adjacent recesses.Then, calculate the mean value of measured shortest distance, thus obtain the interval of recess.In addition, also the maximum value of measured shortest distance can be set to the interval of recess.The interval of recess can be the mean value of shortest distance, also can be the maximum value of shortest distance, but the mean value of preferred shortest distance.
In the present invention, the method of multiple recess and multiple protuberance is formed as at least one surface at intermediate film for laminated glasses, such as, grain roller method can be enumerated, stack method, special-shaped extrusion method, the extruding that make use of melt fracture pat embossing (extrusionlipembossingmethod) etc.Wherein, from the aspect of the recess that easily can obtain this groove shape adjoined shape arranged side by side abreast, preferred grain roller method.
As the grain roller used in above-mentioned grain roller method, such as can enumerate and use the abrasive substance of aluminum oxide, silicon oxide etc. to carry out shot peening to metalling roll surface, then use vertical grinding etc. to rub to reduce the excessive peak on surface, thus make roller surface have the grain roller of embossed channels (concave convex texture).In addition, can also enumerate and use engraving mill and embossed channels (concave convex texture) be transferred to metalling roll surface, thus make roller surface have the grain roller of embossed channels (concave convex texture).Can also enumerate by etching (corrosion) and make roller surface have the grain roller etc. of embossed channels (concave convex texture).
Intermediate film for laminated glasses of the present invention is laminated with the resin layer of more than 2 layers.Such as, as the resin layers of more than 2 layers, there is the first resin layer and the second resin layer, and the first resin layer and the second resin layer have different character, thereby, it is possible to provide have only 1 layer time the intermediate film for laminated glasses of various performances that is difficult to realize.On the other hand, when being laminated with the resin layer of more than 2 layers, the problem of ghost image will be there is.
Preferred above-mentioned resin layer contains thermoplastic resin.
As above-mentioned thermoplastic resin, such as, can enumerate poly(vinylidene fluoride), tetrafluoroethylene, vinylidene difluoride-hexafluoropropylene copolymer, poly-trifluoro-ethylene, acrylonitrile-butadiene-styrene copolymer, polyester, polyethers, polymeric amide, polycarbonate, polyacrylic ester, polymethacrylate, polyvinyl chloride, polyethylene, polypropylene, polystyrene, polyvinyl acetal, ethylene-vinyl acetate copolymer etc.Wherein, above-mentioned resin layer, preferably containing polyvinyl acetal or ethylene-vinyl acetate copolymer, more preferably contains polyvinyl acetal.
Preferred above-mentioned resin layer contains polyvinyl acetal and softening agent.
As above-mentioned softening agent, as long as the general softening agent used in intermediate film for laminated glasses, just be not particularly limited, such as, can enumerate the organic plasticizers such as unitary organic acid acetic, poly-basic organic acid ester, the phosphoric acid softening agent etc. such as organic phosphoric acid compound, organic phosphorons acid compound.
As above-mentioned organic plasticizers, such as, can enumerate triglycol-two-2-ethylhexanoate, triglycol-two-2 Ethylbutanoic acid ester, triglycol-two-positive heptanoate, Tetraglycol 99-two-2-ethylhexanoate, Tetraglycol 99-two-2 Ethylbutanoic acid ester, Tetraglycol 99-two-positive heptanoate, glycol ether-two-2-ethylhexanoate, glycol ether-two-2 Ethylbutanoic acid ester, glycol ether-two-positive heptanoate etc.Wherein, above-mentioned resin layer preferably containing triglycol-two-2-ethylhexanoate, triglycol-two-2 Ethylbutanoic acid ester or triglycol-two-positive heptanoate, more preferably contains triglycol-two-2-ethylhexanoate.
Above-mentioned resin layer is preferably containing bonding force conditioning agent.Especially, when manufacturing laminated glass, preferably above-mentioned bonding force conditioning agent is contained with the resin layer of glass contact.
As above-mentioned bonding force conditioning agent, such as, can use an alkali metal salt or alkaline earth salt.As above-mentioned bonding force conditioning agent, such as, can enumerate the salt of potassium, sodium, magnesium etc.
As forming the acid of above-mentioned salt, such as, can enumerate the organic acid of the carboxylic acids such as sad, caproic acid, 2 Ethylbutanoic acid, butyric acid, acetic acid, formic acid, or the mineral acid such as hydrochloric acid, nitric acid.From the aspect that easily can regulate the bonding force of glass and resin layer when manufacturing laminated glass, preferably contain magnesium salts as bonding force conditioning agent with the resin layer of glass contact.
Above-mentioned resin layer can contain oxidation inhibitor, photostabilizer, the additive such as modified silicon oil, fire retardant, static inhibitor, resistance to humectant, thermal radiation tamper, thermal radiation absorption agent as bonding force conditioning agent as required.
For intermediate film for laminated glasses of the present invention, preferably as more than 2 layers resin layer and at least there is the first resin layer and the second resin layer, and polyvinyl acetal contained by above-mentioned first resin layer is (following, be called polyvinyl acetal A) amount of hydroxyl groups different from the amount of hydroxyl groups of the polyvinyl acetal (hereinafter referred to as polyvinyl acetal B) contained by above-mentioned second resin layer.
Due to the different in kind of polyvinyl acetal A and polyvinyl acetal B, therefore can provide have only 1 layer time the intermediate film for laminated glasses of various performances that is difficult to realize.Such as, between above-mentioned second resin layer of 2 layers, be laminated with above-mentioned first resin layer and the amount of hydroxyl groups of the amount of hydroxyl groups of polyvinyl acetal A lower than polyvinyl acetal B time, there is the tendency of above-mentioned first resin layer and above-mentioned second resin layer Comparatively speaking second-order transition temperature step-down.Its result, above-mentioned first resin layer and the Comparatively speaking deliquescing of above-mentioned second resin layer, the sound-proofing of intermediate film for laminated glasses uprises.In addition, between above-mentioned second resin layer of 2 layers, be laminated with above-mentioned first resin layer and the amount of hydroxyl groups of the amount of hydroxyl groups of polyvinyl acetal A higher than polyvinyl acetal B time, there is above-mentioned first resin layer and the above-mentioned second resin layer Comparatively speaking tendency that uprises of second-order transition temperature.Its result, above-mentioned first resin layer and above-mentioned second resin layer Comparatively speaking hardening, the resistance to penetrability of intermediate film for laminated glasses uprises.
And then, when above-mentioned first resin layer and above-mentioned second resin layer contain softening agent, the content (hereinafter referred to as content A) of the softening agent relative to polyvinyl acetal 100 mass parts preferably in above-mentioned first resin layer is different from the content (hereinafter referred to as content B) of the softening agent relative to polyvinyl acetal 100 mass parts in above-mentioned second resin layer.Such as, between above-mentioned second resin layer of 2 layers, be laminated with above-mentioned first resin layer and above-mentioned content A higher than above-mentioned content B time, there is the tendency of above-mentioned first resin layer and above-mentioned second resin layer Comparatively speaking second-order transition temperature step-down.Its result, above-mentioned first resin layer and the Comparatively speaking deliquescing of above-mentioned second resin layer, the sound-proofing of intermediate film for laminated glasses uprises.In addition, between above-mentioned second resin layer of 2 layers, be laminated with above-mentioned first resin layer and above-mentioned content A lower than above-mentioned content B time, there is above-mentioned first resin layer and the above-mentioned second resin layer Comparatively speaking tendency that uprises of second-order transition temperature.Its result, above-mentioned first resin layer and above-mentioned second resin layer Comparatively speaking hardening, the resistance to penetrability of intermediate film for laminated glasses uprises.
As the combination of the resin layer of more than 2 layers of formation intermediate film for laminated glasses of the present invention, such as, can enumerate the sound-proofing in order to improve laminated glass and combine as the pugging of above-mentioned first resin layer and the protective layer as above-mentioned second resin layer.From the view point of the sound-proofing improving laminated glass, preferred above-mentioned pugging contains polyvinyl acetal X and softening agent, and above-mentioned protective layer contains polyvinyl acetal Y and softening agent.And, when being laminated with above-mentioned pugging between the above-mentioned protective layer of 2 layers, the intermediate film for laminated glasses (hereinafter also referred to sound insulation intermediate coat) with excellent sound-proofing can be obtained.In the present application, though as above-mentioned pugging and above-mentioned protective layer the stacked resin layer of different in kind, also can obtain the intermediate film for laminated glasses of the generation that can prevent ghost image.Below, more specific description is carried out to sound insulation intermediate coat.
In above-mentioned sound insulation intermediate coat, above-mentioned pugging has the effect of giving sound-proofing.
Above-mentioned pugging is preferably containing polyvinyl acetal X and softening agent.
Above-mentioned polyvinyl acetal X is prepared by utilizing aldehyde to make polyvinyl alcohol carry out acetalation.Above-mentioned polyvinyl alcohol obtains by polyvinyl acetate is carried out saponification usually.
The preferred lower limit of the mean polymerisation degree of above-mentioned polyvinyl alcohol is 200, and preferred upper limit is 5000.By the mean polymerisation degree of above-mentioned polyvinyl alcohol is set to more than 200, thus the resistance to penetrability of the sound insulation intermediate coat of gained can being improved, by being set to less than 5000, thus the formability of pugging can be guaranteed.The preferred lower limit of the mean polymerisation degree of above-mentioned polyvinyl alcohol is 500, and the preferred upper limit is 4000.
It should be noted that, the mean polymerisation degree of above-mentioned polyvinyl alcohol is obtained by the method based on JISK6726 " polyvinyl alcohol test method ".
Be 4 for above-mentioned polyvinyl alcohol being carried out the preferred lower limit of the carbon number of the aldehyde of acetalation, preferred upper limit is 6.By the carbon number of aldehyde is set to more than 4, thus stably can contain the softening agent of substantial amount, excellent sound-proofing properties can have been given play to.Further, oozing out of softening agent can be prevented.By the carbon number of aldehyde is set to less than 6, thus the synthesis of polyvinyl acetal X can be made to become easy, can productivity be guaranteed.
Be the aldehyde of 4 ~ 6 as above-mentioned carbon number, can be the aldehyde of straight-chain, also can be the aldehyde of branched, such as butyraldehyde-n, valeraldehyde etc. can be enumerated.
The preferred upper limit of the amount of hydroxyl groups of above-mentioned polyvinyl acetal X is 30 % by mole.By the amount of hydroxyl groups of above-mentioned polyvinyl acetal X is set to less than 30 % by mole, thus it can be made to contain the softening agent having given play to sound-proofing aequum, oozing out of softening agent can be prevented.More preferably the upper limit of the amount of hydroxyl groups of above-mentioned polyvinyl acetal X is 28 % by mole, further preferred upper limit is 26 % by mole, and particularly preferably the upper limit is 24 % by mole, and preferred lower limit is 10 % by mole, more preferably lower limit is 15 % by mole, and further preferred lower limit is 20 % by mole.
The amount of hydroxyl groups of above-mentioned polyvinyl acetal X is the value represented with percentage (% by mole) by the mole fraction that the ethene base unit weight of hydroxyl institute bonding is tried to achieve divided by total ethene base unit weight of main chain.The ethene base unit weight of above-mentioned hydroxyl institute bonding is such as tried to achieve by measuring the ethene base unit weight of the hydroxyl institute bonding of above-mentioned polyvinyl acetal X based on the method for JISK6728 " polyvinyl butyral acetal test method ".
The preferred lower limit of the acetal base unit weight of above-mentioned polyvinyl acetal X is 60 % by mole, and preferred upper limit is 85 % by mole.By the acetal base unit weight of above-mentioned polyvinyl acetal X is set to more than 60 % by mole, thus improve the hydrophobicity of pugging, it can be made to contain the softening agent having given play to sound-proofing aequum, the oozing out of softening agent, albefaction can be prevented.By the acetal base unit weight of above-mentioned polyvinyl acetal X is set to less than 85 % by mole, thus make the synthesis transfiguration of polyvinyl acetal X easy, can productivity be guaranteed.The lower limit of the acetal base unit weight of above-mentioned polyvinyl acetal X is more preferably 65 % by mole, more preferably more than 68 % by mole.
Above-mentioned acetal base unit weight is tried to achieve by measuring the ethene base unit weight of the acetal radical institute bonding of above-mentioned polyvinyl acetal X based on the method for JISK6728 " polyvinyl butyral acetal test method ".
The preferred lower limit of the acetyl base unit weight of above-mentioned polyvinyl acetal X is 0.1 % by mole, and preferred upper limit is 30 % by mole.By the acetyl base unit weight of above-mentioned polyvinyl acetal X is set to more than 0.1 % by mole, thus it can be made to contain the softening agent having given play to sound-proofing aequum, can prevent from oozing out.In addition, by the acetyl base unit weight of above-mentioned polyvinyl acetal X is set to less than 30 % by mole, thus the hydrophobicity of pugging can be improved, can albefaction be prevented.More preferably the lower limit of above-mentioned acetyl base unit weight is 1 % by mole, and further preferred lower limit is 5 % by mole, and particularly preferably lower limit is 8 % by mole, and more preferably the upper limit is 25 % by mole, and further preferred upper limit is 20 % by mole.Above-mentioned acetyl base unit weight is the value that mole fraction that the value ethene base unit weight of the ethene base unit weight and hydroxyl institute bonding that deduct acetal radical institute bonding from total ethene base unit weight of main chain obtained obtains divided by total ethene base unit weight of main chain is represented with percentage (% by mole).
Particularly; from making in above-mentioned pugging easily containing the aspect of softening agent having given play to sound-proofing aequum, preferred above-mentioned polyvinyl acetal X to be above-mentioned acetyl base unit weight the be polyvinyl acetal of more than 8 % by mole or above-mentioned acetyl base unit weight are less than 8 % by mole and acetal base unit weight is the polyvinyl acetal of more than 65 % by mole.In addition, more preferably above-mentioned polyvinyl acetal X to be above-mentioned acetyl base unit weight the be polyvinyl acetal of more than 8 % by mole or above-mentioned acetyl base unit weight are less than 8 % by mole and acetal base unit weight is the polyvinyl acetal of more than 68 % by mole.
The content of the softening agent in above-mentioned pugging is 45 mass parts relative to the preferred lower limit of above-mentioned polyvinyl acetal X100 mass parts, and preferred upper limit is 80 mass parts.By the content of above-mentioned softening agent is set to more than 45 mass parts, thus higher sound-proofing can have been given play to, by being set to below 80 mass parts, thus can prevent from causing the transparency of intermediate film for laminated glasses, the situation of cementability reduction because there is oozing out of softening agent.More preferably the lower limit of the content of above-mentioned softening agent is 50 mass parts, and further preferred lower limit is 55 mass parts, and more preferably the upper limit is 75 mass parts, and further preferred upper limit is 70 mass parts.
The preferred lower limit of the thickness of above-mentioned pugging is 0.05mm.By the thickness of above-mentioned pugging is set to more than 0.05mm, thus sufficient sound-proofing can be given play to.More preferably the lower limit of the thickness of above-mentioned pugging is 0.08mm.It should be noted that, the upper limit is not particularly limited, if but consider the thickness as intermediate film for laminated glasses, then preferred upper limit is 0.3mm.
Above-mentioned protective layer has following effects: prevent from making because of a large amount of the oozing out of softening agent contained by pugging the situation that the cementability of intermediate film for laminated glasses and glass declines, and give resistance to penetrability to intermediate film for laminated glasses.
Above-mentioned protective layer, such as preferably containing polyvinyl acetal Y and softening agent, more preferably contains the amount of hydroxyl groups polyvinyl acetal Y larger than polyvinyl acetal X and softening agent.
Above-mentioned polyvinyl acetal Y can carry out acetalation by being utilized by polyvinyl alcohol aldehyde and prepare.
Above-mentioned polyvinyl alcohol obtains by polyvinyl acetate is carried out saponification usually.
In addition, the preferred lower limit of the mean polymerisation degree of above-mentioned polyvinyl alcohol is 200, and preferred upper limit is 5000.By the mean polymerisation degree of above-mentioned polyvinyl alcohol is set to more than 200, thus the resistance to penetrability of intermediate film for laminated glasses can being improved, by being set to less than 5000, thus the formability of protective layer can be guaranteed.More preferably the lower limit of the mean polymerisation degree of above-mentioned polyvinyl alcohol is 500, and more preferably the upper limit is 4000.
Be 3 for above-mentioned polyvinyl alcohol being carried out the preferred lower limit of the carbon number of the aldehyde of acetalation, preferred upper limit is 4.By the carbon number of aldehyde is set to more than 3, thus the resistance to penetrability of intermediate film for laminated glasses is uprised.By the carbon number of aldehyde is set to less than 4, thus the productivity of polyvinyl acetal Y is improved.
Be the aldehyde of 3 ~ 4 as above-mentioned carbon number, can be the aldehyde of straight-chain, also can be the aldehyde of branched, include, for example butyraldehyde-n etc.
The preferred upper limit of the amount of hydroxyl groups of above-mentioned polyvinyl acetal Y is 33 % by mole, and preferred lower limit is 28 % by mole.By the amount of hydroxyl groups of above-mentioned polyvinyl acetal Y is set to less than 33 % by mole, thus the albefaction of intermediate film for laminated glasses can be prevented.By the amount of hydroxyl groups of above-mentioned polyvinyl acetal Y is set to more than 28 % by mole, thus the resistance to penetrability of intermediate film for laminated glasses is uprised.
The preferred lower limit of the acetal base unit weight of above-mentioned polyvinyl acetal Y is 60 % by mole, and preferred upper limit is 80 % by mole.By above-mentioned acetal base unit weight is set to more than 60 % by mole, thus it can be made to contain the softening agent having given play to the sufficient aequum of resistance to penetrability.By above-mentioned acetal base unit weight is set to less than 80 % by mole, thus the bonding force of above-mentioned protective layer and glass can be guaranteed.More preferably the lower limit of above-mentioned acetal base unit weight is 65 % by mole, and more preferably the upper limit is 69 % by mole.
The preferred upper limit of the acetyl base unit weight of above-mentioned polyvinyl acetal Y is 7 % by mole.By the acetyl base unit weight of above-mentioned polyvinyl acetal Y is set to less than 7 % by mole, thus the hydrophobicity of protective layer can be improved and prevent albefaction.More preferably the upper limit of above-mentioned acetyl base unit weight is 2 % by mole, and preferred lower limit is 0.1 % by mole.It should be noted that, the amount of hydroxyl groups of polyvinyl acetal A, B and Y, acetal base unit weight and acetyl base unit weight can utilize the method same with polyvinyl acetal X to measure.
The content of the softening agent in above-mentioned protective layer is 20 mass parts relative to the preferred lower limit of above-mentioned polyvinyl acetal Y100 mass parts, and preferred upper limit is 45 mass parts.By the content of above-mentioned softening agent is set to more than 20 mass parts, thus resistance to penetrability can being guaranteed, by being set to below 45 mass parts, thus oozing out of softening agent can be prevented, the transparency of intermediate film for laminated glasses, the reduction of cementability can be prevented.More preferably the lower limit of the content of above-mentioned softening agent is 30 mass parts, and further preferred lower limit is 35 mass parts, and more preferably the upper limit is 43 mass parts, and further preferred upper limit is 41 mass parts.From the aspect that the sound-proofing of laminated glass improves further, the content of the softening agent in preferred above-mentioned protective layer is fewer than the content of the softening agent in above-mentioned pugging.
From the aspect that the sound-proofing of laminated glass improves further, the amount of hydroxyl groups of preferably polyethylene acetal Y is larger than the amount of hydroxyl groups of polyvinyl acetal X, more preferably go out greatly more than 1 % by mole, preferably go out greatly more than 5 % by mole further, particularly preferably go out greatly more than 8 % by mole.By adjusting the amount of hydroxyl groups of polyvinyl acetal X and polyvinyl acetal Y, thus the content of the softening agent in above-mentioned pugging and above-mentioned protective layer can be controlled, the second-order transition temperature step-down of above-mentioned pugging.Consequently, the sound-proofing of laminated glass improves further.
In addition, from the aspect that the sound-proofing of laminated glass improves further, the softening agent in preferred above-mentioned pugging relative to the content of polyvinyl acetal X100 mass parts (hereinafter also referred to content X.) than the softening agent in above-mentioned protective layer relative to the content of polyvinyl acetal Y100 mass parts (hereinafter also referred to as content Y.) many, more preferably have more more than 5 mass parts, preferably have more more than 15 mass parts further, particularly preferably have more more than 20 mass parts.By adjustment content X and content Y, thus the second-order transition temperature step-down of above-mentioned pugging.Consequently, the sound-proofing of laminated glass improves further.
Preferred lower limit as the thickness of above-mentioned protective layer is 0.2mm, and preferred upper limit is 3mm.By the thickness of above-mentioned protective layer is set to more than 0.2mm, thus resistance to penetrability can be guaranteed.
More preferably the lower limit of the thickness of above-mentioned protective layer is 0.3mm, and more preferably the upper limit is 1.5mm, and further preferred upper limit is 0.5mm, and particularly preferably the upper limit is 0.4mm.
As the method manufacturing above-mentioned sound insulation intermediate coat, be not particularly limited, such as, above-mentioned pugging and protective layer passed through the common masking legal system slabbings such as extrusion process, rolling process, impact molding, carries out stacked method etc. thereafter.
In addition, following intermediate film for laminated glasses also belongs to one of the present invention, it is the intermediate film for laminated glasses being laminated with pugging between the protective layer of 2 layers, wherein, softening agent 45 ~ 80 mass parts is contained relative to polyvinyl acetal 100 mass parts in above-mentioned pugging, softening agent 20 ~ 45 mass parts is contained relative to polyvinyl acetal 100 mass parts in above-mentioned protective layer, on at least one surface of above-mentioned protective layer, there is multiple recess and multiple protuberance, above-mentioned recess has bottom ditch shape continuously, adjacent above-mentioned recess is arranged side by side abreast, the trench depth (Rzg) with the recess measured based on JISB-0601 (1994) on the surface of multiple recess and multiple protuberance of above-mentioned protective layer is 10 ~ 40 μm, when selecting any one recess, this recess and and the interval of a recess that adjoins of this recess, with this recess and and the difference at the interval of another recess that adjoins of this recess more than 50 μm, and adjacent recess be spaced apart less than 1000 μm.
It should be noted that; in the present invention; " at least one surface of protective layer, there is multiple recess and multiple protuberance " and also mean " being formed with multiple recess and multiple protuberance at least one surface of protective layer "; " recess has bottom ditch shape continuously; adjacent above-mentioned recess is arranged side by side abreast " also means " recess has bottom ditch shape continuously, and adjacent above-mentioned recess is formed abreast ".
In addition, the laminated glass being laminated with intermediate film for laminated glasses of the present invention between a pair sheet glass also belongs to one of the present invention.
Above-mentioned sheet glass can use normally used transparent plate glass.Such as, the unorganic glasses such as float glass process sheet glass, polished plate glass, molded plate glass (moldedplateglass), wired glass (wiredglass), wired sheet glass (wire-reinforcedplateglass), painted sheet glass, thermal radiation absorption glass, heat-radiation reflective glass, raw glass can be enumerated.In addition, the surface that also can be used in glass has the UV-preventing glass of UV-preventing coat.And, also can use the organic plastic plate of polyethylene terephthalate, polycarbonate, polyacrylic ester etc.
As above-mentioned sheet glass, sheet glass of more than two kinds can be used.Such as, can enumerate at clear float sheet glass and give birth to the laminated glass being laminated with intermediate film for laminated glasses of the present invention between the so painted sheet glass of glass.Further, as above-mentioned sheet glass, the sheet glass that thickness of more than two kinds is different can be used.
As the manufacture method of laminated glass of the present invention, be not particularly limited, known manufacture method can be used.
Invention effect
According to the present invention, a kind of intermediate film for laminated glasses can be provided and comprise the laminated glass of this intermediate film for laminated glasses, described intermediate film for laminated glasses is the intermediate film for laminated glasses of the resin layer being laminated with more than 2 layers, it has excellent out gassing in the manufacturing process of laminated glass, and can prevent the generation of ghost image.
Accompanying drawing explanation
Fig. 1 represents that the continuous ditch shape in bottom and recess are at equal intervals and adjacent recess is listed in the schematic diagram of an example of the intermediate film for laminated glasses on surface abreast.
Fig. 2 represents that the continuous ditch shape in bottom and recess are at equal intervals and adjacent recess is listed in the mode chart of an example of the intermediate film for laminated glasses on surface abreast.
Fig. 3 is the schematic diagram of an example of the pattern of the recess representing the groove shape that the surface of intermediate film for laminated glasses has.
Embodiment
Below, enumerate embodiment and come to further describe embodiments of the present invention, but the present invention is not limited to these embodiments.
(embodiment 1)
(1) modulation of pugging resin combination
Relative to utilize butyraldehyde-n make mean polymerisation degree be 2400 polyvinyl butyral acetal (acetyl base unit weight 12 % by mole, butyral base unit weight 66 % by mole, amount of hydroxyl groups 22 % by mole) 100 mass parts that obtain of polyvinyl alcohol generation acetalation; add triglycol-two-2-ethylhexanoate (3GO) 60 mass parts as softening agent; utilize dispersion roller to carry out fully mixing, obtain pugging resin combination.
(2) modulation of protective layer used resin combination
Relative to utilize butyraldehyde-n make mean polymerisation degree be 1700 polyvinyl alcohol carry out polyvinyl butyral acetal (acetyl base unit weight 1 % by mole, butyral base unit weight 69 % by mole, amount of hydroxyl groups 30 % by mole) 100 mass parts that acetalation obtains; add triglycol-two-2-ethylhexanoate (3GO) 40 mass parts as softening agent; utilize dispersion roller to carry out fully mixing, obtain protective layer used resin combination.
(3) making of intermediate film for laminated glasses
Utilize co-extrusion press to carry out coextrusion to obtained pugging resin combination and protective layer used resin combination, thus obtain sequentially laminated with the A layer (protective layer) of the thickness formed by protective layer used resin combination 350 μm, the B layer (pugging) of thickness 100 μm formed by pugging resin combination and the intermediate film for laminated glasses (sound insulation intermediate coat) of the 3-tier architecture of the C layer (protective layer) of thickness 350 μm that formed by protective layer used resin combination.
(4) concavo-convex imparting
As the first operation, in the following sequence at the random concaveconvex shape of two sides transfer printing of intermediate film for laminated glasses.First, abrasive material is used to impose random concavo-convex to iron roll surface, then vertical grinding is carried out to this iron roll, and then it is fine concavo-convex to use finer abrasive material to impose the par after grinding, thus obtains 1 pair roller of the same shape with thick main embossing and fine secondary embossing.This 1 pair roller is used as concaveconvex shape transfer device, to the random concaveconvex shape of two sides transfer printing of obtained intermediate film for laminated glasses.As transfer printing condition now, the temperature of intermediate film for laminated glasses is set to 80 DEG C, the temperature of above-mentioned roller is set to 145 DEG C, linear speed is set to 10m/min, the wide 1.5m of being set to of film, stamping pressure is set to 10 ~ 200kN/m.For the surfaceness of the intermediate film for laminated glasses after figuration, utilize 10 mean roughness Rz of JISB0601 (1994) to measure, its result is 20 μm.Mensuration is that the numerary signal recorded by using surface roughness measurement device (Inc. of little Ban institute, SE1700 α) is carried out data processing and carried out.Measure direction and be set to vertical direction relative to groove, measure under the condition of tip radius=2 of cutoff (cut-offvalue)=2.5mm, datum length=2.5mm, evaluation length=12.5mm, contact pilotage μm, tip angle=60 °, finding speed=0.5mm/s.
As the second operation, impart the concavo-convex of bottom ditch shape (groove shape) continuously by the surface of following order to intermediate film for laminated glasses.The pair of rolls be made up of the metallic roll after using trilateral bias type grinding machine effects on surface to impose milling processing and the rubber rollers of JIS hardness with 45 ~ 75 is used as concaveconvex shape transfer device, to make through the first operation transferred with the intermediate film for laminated glasses of random concaveconvex shape by this concaveconvex shape transfer device, it is concavo-convex that the recess imparted on the surface of the A layer of intermediate film for laminated glasses as bottom ditch shape continuously (groove shape) is formed in parallel and equidistantly.As transfer printing condition now, the temperature of intermediate film for laminated glasses is set to normal temperature, roll temperature is set to 130 DEG C, and linear speed is set to 10m/min, and stamping pressure is set to 500kPa.
Then, same operation is also implemented to the surface of the C layer of intermediate film for laminated glasses, impart the recess for bottom ditch shape continuously (groove shape).Now, be set to the recess for bottom ditch shape continuously (groove shape) given in the surface of A layer and become 10 ° with the intersecting angle given in the recess for bottom ditch shape continuously (groove shape) on the surface of C layer.
(5) the concavo-convex mensuration on A layer and C layer surface
Use opticmicroscope (SONIC Inc., BS-8000III), observe the A layer of intermediate film for laminated glasses and the surface (range of observation 20mm × 20mm) of C layer of gained, measure the interval of adjacent recess, the mean value of the shortest distance between the bottommost calculating adjacent recess, obtains the interval of recess thus.The recess on the surface of A layer and C layer according to 1000 μm, 900 μm, 1000 μm, 900 μm ... pattern spaced and parallel ground side by side.That is, when selecting any one recess, this recess and and a recess adjoining of this recess interval, with this recess and and the difference at the interval of another recess that adjoins of this recess be 100 μm.
In addition, the trench depth (Rzg) of the recess on the A layer of the intermediate film for laminated glasses of gained and the surface of C layer is that the datum length of JISB-0601 (1994) " surfaceness-definition and expression " defined is set to 2.5mm, the trench depth that to calculate with the average line of roughness curve (becoming the line that minimum mode sets according to the sum of squares of the deviation to roughness curve) be benchmark, using the mean value of the trench depth of measured ditch number as the trench depth in each datum length, get the mean value at 5 places of the trench depth in each datum length.The ditch number of above-mentioned A layer is 3, the ditch number of above-mentioned C layer is 3.In addition, the trench depth (Rzg) of the above-mentioned recess on the surface of A layer and C layer obtains by the numerary signal used measured by surface roughness measurement device (Inc. of little Ban institute, SE1700 α) is carried out data processing.Being set to vertical direction relative to groove by measuring direction, measuring under the condition of tip radius=2 of contact pilotage μm, tip angle=60 °, finding speed=0.5mm/s.The trench depth (Rzg) of the recess on the surface of A layer is 22 μm, the trench depth of the recess on the surface of C layer (Rzg) is 18 μm.
(embodiment 2 ~ 11)
The interval of recess on A layer and C layer surface and the trench depth (Rzg) of recess are set according to the mode shown in table 1,2, in addition, utilizes method similarly to Example 1 to make intermediate film for laminated glasses.
(embodiment 12 ~ 15)
The content of the acetyl base unit weight of the polyvinyl butyral acetal used in protective layer and pugging, butyral base unit weight and amount of hydroxyl groups and softening agent is changed according to the mode shown in table 1,2; the interval of recess on A layer and C layer surface and the trench depth (Rzg) of recess are set according to the mode shown in table 1,2; in addition, method is similarly to Example 1 utilized to make intermediate film for laminated glasses.It should be noted that, the polyvinyl butyral acetal used in protective layer and pugging utilizes butyraldehyde-n to carry out acetalation to the polyvinyl alcohol that mean polymerisation degree is 1700 and obtains.
(comparative example 1 ~ 4)
The interval of recess on A layer and C layer surface and the trench depth (Rzg) of recess are set to as shown in table 1,2, in addition, have made intermediate film for laminated glasses by method similarly to Example 1.
(evaluation)
For the intermediate film for laminated glasses of gained in embodiment and comparative example, evaluated by following method.
Result is shown in table 1,2.In table, Buization degree represents butyral base unit weight, and OHization degree represents amount of hydroxyl groups, and Acization degree represents acetyl base unit weight, and softening agent number represents the content of the softening agent relative to polyvinyl butyral acetal 100 mass parts.
(1) evaluation of out gassing
Use gained at the irregular intermediate film for laminated glasses of surperficial tool, as described below, to reduce pressure, degassing method crimps in advance, then carries out main crimping, has made laminated glass.
(decompression degassing method)
Between the transparency glass plate (vertical 30cm × horizontal 30cm × thick 2.5mm) intermediate coat being sandwiched in two pieces, cut the part had more, the laminated glass structure (duplexer) obtained thus is moved on in rubber bag, rubber bag is connected to suction negative booster, while carrying out heating, maintenance 10 minutes under the decompression of-60kPa (absolute pressure 16kPa), after the temperature (precompressed jointing temp) being heated to laminated glass structure (duplexer) reaches 70 DEG C, return to normal atmosphere and terminate pre-crimping.It should be noted that, degassed beginning temperature during above-mentioned pre-crimping is carried out under 3 conditions of 40 DEG C, 50 DEG C and 60 DEG C.
(main crimping)
Laminated glass structure (duplexer) after crimping utilizing aforesaid method in advance puts into autoclave, keep under the condition of temperature 140 DEG C, pressure 1300kPa after 10 minutes, be cooled to 50 DEG C, return to normal atmosphere and terminate main crimping, make laminated glass.
(the baking test of laminated glass)
The laminated glass obtained is heated 2 hours in the baking oven of 140 DEG C.Then, take out from baking oven, place and cool for 3 hours, the then outward appearance of visual observations laminated glass.For each 20 pieces, checked piece number creating foaming (bubble) between sheet glass and intermediate film for laminated glasses, the average evaluation being less than 5 pieces by piece number that foams under all conditions is "○", and the average evaluation being more than 6 pieces by foaming piece number is "×".
(2) evaluation of ghost image generation
Light source employs 10W quartz electricbulb (rising sun photoelectricity machine Inc., PS55E26110V-10W, total light flux 70lm).Above-mentioned 10W quartz electricbulb is assumed to the light source of the general brightness of the window-glass can injecting automobile, aircraft, buildings etc.By the method based on JISR3212 (2008), have rated the generation with or without ghost image.It should be noted that, the situation that there occurs the image being greater than 6.5 points is judged as there occurs ghost image, the situation of the image that there occurs less than 6.5 points is judged as there occurs single image.Consequently, by observing the average evaluation of single image of less than 3.5 points for " 00 ", observing and be greater than 3.5 points and the average evaluation of the single image of less than 6.5 points is "○", is "×" by the average evaluation that there occurs ghost image.
It should be noted that, real vehicle setting angle be set to 20 ° and measure.In addition, be configured to the angle in 5 ° between the recess of the groove shape given in the surface of A layer and horizontal direction, give the angle in-5 ° between the recess of the groove shape in the surface of C layer and horizontal direction.
[table 1]
[table 2]
Utilizability in industry
According to the present invention, intermediate film for laminated glasses can be provided and comprise the laminated glass of this intermediate film for laminated glasses, described intermediate film for laminated glasses is the intermediate film for laminated glasses of the resin layer being laminated with more than 2 layers, it has excellent out gassing in the manufacturing process of laminated glass, and can prevent the generation of ghost image.
Nomenclature
A 1 optional recess
2 recesses adjacent with an optional recess
3 recesses adjacent with an optional recess
The interval of A recess 1 and recess 2
The interval of B recess 1 and recess 3
Claims (6)
1. an intermediate film for laminated glasses, is characterized in that,
It is the intermediate film for laminated glasses of the resin layer being laminated with more than 2 layers, wherein,
Have multiple recess and multiple protuberance at least one surface, described recess has bottom ditch shape continuously, and adjacent described recess is arranged side by side abreast,
The trench depth of the recess that described foundation JISB-0601 (1994) with the surface of multiple recess and multiple protuberance measures is expressed as 10 ~ 40 μm with Rzg, when selecting any one recess, this recess and and a recess adjoining of this recess interval, with this recess and and the difference at the interval of another recess that adjoins of this recess more than 50 μm, and adjacent recess be spaced apart less than 1000 μm.
2. intermediate film for laminated glasses according to claim 1, is characterized in that, resin layer contains polyvinyl acetal and softening agent.
3. intermediate film for laminated glasses according to claim 2, it is characterized in that, at least have the first resin layer and the second resin layer, the amount of hydroxyl groups of the polyvinyl acetal comprised in described first resin layer is different from the amount of hydroxyl groups of the polyvinyl acetal comprised in described second resin layer.
4. intermediate film for laminated glasses according to claim 2, it is characterized in that, the content of the softening agent relative to polyvinyl acetal 100 mass parts in the first resin layer is different from the content of the softening agent relative to polyvinyl acetal 100 mass parts in the second resin layer.
5. an intermediate film for laminated glasses, is characterized in that,
It is the intermediate film for laminated glasses that pugging is laminated between two-layer protective layer, wherein,
Contain softening agent 45 ~ 80 mass parts relative to polyvinyl acetal 100 mass parts in described pugging, in described protective layer, contain softening agent 20 ~ 45 mass parts relative to polyvinyl acetal 100 mass parts,
Have multiple recess and multiple protuberance at least one surface of described protective layer, described recess has bottom ditch shape continuously, and adjacent described recess is arranged side by side abreast,
Described protective layer there is the surface of multiple recess and multiple protuberance, the trench depth of recess that measures according to JISB-0601 (1994) is expressed as 10 ~ 40 μm with Rzg; when selecting any one recess; this recess and and a recess adjoining of this recess interval, with this recess and and the difference at the interval of another recess that adjoins of this recess more than 50 μm, and adjacent recess be spaced apart less than 1000 μm.
6. a laminated glass, is characterized in that, the intermediate film for laminated glasses according to any one of claim 1 to 5 is laminated between a pair sheet glass.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-160503 | 2013-08-01 | ||
| JP2013160503 | 2013-08-01 | ||
| PCT/JP2014/070405 WO2015016366A1 (en) | 2013-08-01 | 2014-08-01 | Laminated glass interlayer and laminated glass |
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| Publication Number | Publication Date |
|---|---|
| CN105377787A true CN105377787A (en) | 2016-03-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480039947.1A Pending CN105377787A (en) | 2013-08-01 | 2014-08-01 | Laminated glass interlayer and laminated glass |
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| Country | Link |
|---|---|
| US (1) | US20160129674A1 (en) |
| EP (1) | EP3029003A4 (en) |
| JP (1) | JP6522943B2 (en) |
| KR (1) | KR20160039147A (en) |
| CN (1) | CN105377787A (en) |
| MX (1) | MX2016001068A (en) |
| RU (1) | RU2657566C2 (en) |
| WO (1) | WO2015016366A1 (en) |
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| MX2016008883A (en) | 2014-03-31 | 2016-09-16 | Sekisui Chemical Co Ltd | Interlayer film for laminated glass, and laminated glass. |
| US11565507B2 (en) * | 2014-04-09 | 2023-01-31 | Sekisui Chemical Co., Ltd. | Laminated-glass intermediate film, rolled body, laminated glass, and method for producing laminated glass |
| EP4385728A2 (en) * | 2014-09-30 | 2024-06-19 | Sekisui Chemical Co., Ltd. | Interlayer film for laminated glass, and laminated glass |
| AU2016246965A1 (en) | 2015-04-08 | 2017-10-12 | Sekisui Chemical Co., Ltd. | Interlayer for laminated glass and laminated glass |
| KR102030915B1 (en) * | 2015-04-10 | 2019-10-10 | 세키스이가가쿠 고교가부시키가이샤 | Interlayer for laminated glass, laminated glass, and production method for interlayer for laminated glass |
| WO2016163512A1 (en) * | 2015-04-10 | 2016-10-13 | 積水化学工業株式会社 | Interlayer for laminated glass, laminated glass, production method for embossing roll, and production method for interlayer for laminated glass |
| WO2017022686A1 (en) * | 2015-07-31 | 2017-02-09 | 積水化学工業株式会社 | Intermediate film for laminated glass, method for producing intermediate film for laminated glass, and laminated glass |
| BR112018072949A2 (en) * | 2016-07-20 | 2019-02-19 | Sekisui Chemical Co., Ltd | poly (vinyl acetal) porous object and poly (vinyl acetal) nonwoven |
| CN109983096A (en) | 2016-11-24 | 2019-07-05 | 日本瑞翁株式会社 | Bonding agent sheet material and laminated glass |
| CN109641423B (en) | 2017-05-24 | 2022-06-24 | 法国圣戈班玻璃厂 | Composite glass sheet and method for manufacturing the same |
| WO2020007610A1 (en) * | 2018-07-02 | 2020-01-09 | Saint-Gobain Glass France | Wedge-shaped multi-ply intermediate layer with acoustically damping properties |
| KR102317124B1 (en) * | 2019-08-23 | 2021-10-22 | 에스케이씨 주식회사 | Film for bonding and light transmitting layered product comprising of the same |
| DE112020003804T5 (en) | 2019-08-09 | 2022-04-28 | Skc Co., Ltd. | FILM FOR BONDING AND TRANSLUCENT LAMINATE WITH THIS FILM |
| KR102317548B1 (en) * | 2019-08-27 | 2021-10-25 | 에스케이씨 주식회사 | Film for bonding and light transmitting layered product comprising of the same |
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Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2015016366A1 (en) | 2017-03-02 |
| WO2015016366A1 (en) | 2015-02-05 |
| RU2657566C2 (en) | 2018-06-14 |
| KR20160039147A (en) | 2016-04-08 |
| RU2016107172A3 (en) | 2018-04-03 |
| MX2016001068A (en) | 2016-04-26 |
| EP3029003A1 (en) | 2016-06-08 |
| EP3029003A4 (en) | 2017-03-22 |
| US20160129674A1 (en) | 2016-05-12 |
| RU2016107172A (en) | 2017-09-06 |
| JP6522943B2 (en) | 2019-05-29 |
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